CN115872772B - Preparation method of fly ash-based ceramic membrane support - Google Patents
Preparation method of fly ash-based ceramic membrane support Download PDFInfo
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- CN115872772B CN115872772B CN202211731364.8A CN202211731364A CN115872772B CN 115872772 B CN115872772 B CN 115872772B CN 202211731364 A CN202211731364 A CN 202211731364A CN 115872772 B CN115872772 B CN 115872772B
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- 239000010881 fly ash Substances 0.000 title claims abstract description 87
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 239000002383 tung oil Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 235000011187 glycerol Nutrition 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002689 soil Substances 0.000 claims description 8
- 229920002261 Corn starch Polymers 0.000 claims description 7
- 229920001732 Lignosulfonate Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000008120 corn starch Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000010438 granite Substances 0.000 claims description 2
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 12
- 239000002245 particle Substances 0.000 description 26
- 238000005303 weighing Methods 0.000 description 22
- 238000005336 cracking Methods 0.000 description 13
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- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 5
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003906 humectant Substances 0.000 description 4
- 230000003020 moisturizing effect Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241001408630 Chloroclystis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 silicon (aluminum) oxygen Chemical compound 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of a fly ash-based ceramic membrane support body, which comprises the following steps: 1) Performing alkaline washing and acid washing treatment on the fly ash to obtain pretreated fly ash; 2) Mixing the raw materials including the pretreated fly ash, and ageing and extrusion molding to obtain a green body; 3) After spraying a surface water-retaining agent (comprising glycerol, tung oil, dihydric alcohol and polyethylene glycol) on the surface of a green body, standing and curing in a constant temperature and humidity environment, and drying and sintering after curing is finished.
Description
Technical Field
The invention relates to a preparation method of a ceramic membrane support, in particular to a preparation method of a fly ash-based ceramic membrane support, and belongs to the technical field of ceramic materials.
Background
At present, the raw materials for preparing the ceramic membrane support are mainly prepared from high-purity Al 2 O 3 、SiO 2 、ZrO 2 Etc. are aimed at, but Al 2 O 3 、ZrO 2 And the cost of raw materials is high, the sintering temperature is high, and the preparation cost is high. In order to improve this situation, many studies have been made at home and abroad to prepare a porous ceramic matrix using tailings or mineral raw materials as starting materials.
Related researches show that the fly ash contains a large amount of active silicon (aluminum) oxygen tetrahedron, abundant metal oxide useful components and useful properties which are not recognized and yet to be discovered, and the resources and material properties are obvious; the method is characterized in that a large amount of metallurgical slag and tailings are compounded and used for preparing ceramic membranes, so that the problems of environmental pollution of water bodies, atmosphere, soil and the like in mining areas and occupied land caused by stacking industrial solid wastes can be solved, waste materials can be changed into valuable materials, porous ceramics with high performance and high added value are obtained by utilizing the solid wastes, and the large amount, high value, high efficiency and safety utilization of the solid wastes can be realized.
However, there are still many problems in preparing ceramic membrane supports from fly ash. Firstly, the fly ash is used as the dust collected after the coal is burnt at high temperature, and contains a large number of glass beads with different sizes, and the existence of the beads makes the deviation of the melting temperature range of the fly ash worse and not easy to control; moreover, the effect of pore-forming by stacking the support particles is easy to be weakened, and the porosity is influenced. Secondly, the fly ash contains high unburned carbon residue, a layer of hydrophobic film is formed on the surfaces of carbon particles in the mixing process, so that the infiltration of moisture is affected, the water demand of pugs is increased, and cracking is easy to generate in the drying process after molding; meanwhile, the thermal stress cracking is caused by high residual carbon and easy local self-combustion in the sintering process.
Disclosure of Invention
Aiming at the defects existing in the process of preparing the ceramic membrane support by using the fly ash in the prior art, the invention aims to provide a preparation method of the fly ash-based ceramic membrane support, which can improve the molding property of fly ash particles, reduce the influence of glass beads on sintering, prevent cracking in the molding and sintering processes of a green body, and simultaneously use a special surface water-retaining agent in the curing and drying processes, so that the problem of cracking caused by inconsistent internal and external drying rates of the green body can be avoided, and the ceramic membrane support with high molding qualification rate and good appearance quality can be obtained.
In order to achieve the technical aim, the invention also provides a preparation method of the fly ash-based ceramic membrane support body, which comprises the following steps:
1) Performing alkaline washing and acid washing treatment on the fly ash to obtain pretreated fly ash;
2) Mixing the raw materials including the pretreated fly ash, and ageing and extrusion molding to obtain a green body;
3) Spraying a surface water-retaining agent on the surface of the green body, standing and curing in a constant temperature and humidity environment, and drying and sintering after curing; the surface water-retaining agent comprises glycerol, tung oil, dihydric alcohol and polyethylene glycol.
The key of the technical scheme of the invention is as follows: on one hand, the fly ash is washed, and through alkali washing and acid washing, iron, calcium and other metals or alkaline oxides and carbon particles in the fly ash raw materials can be removed, the surfaces of raw fly ash particles are smooth and compact, the surfaces of the treated fly ash particles become rough, a plurality of grooves and holes are formed, the specific surface area of the particles is increased, the particles are convenient to contact, a sintering phase is easy to form during sintering, the sintering temperature can be reduced, meanwhile, the silicate glass network in the fly ash can be directly damaged, the effect of the glass beads is obvious, and the influence of the glass beads on sintering can be effectively avoided. The order of alkali washing and then acid washing is also important, since K remains from alkali washing 2 O、Na 2 The existence of O and the like can lead to the decomposition of mullite formed in the sintering process to form nepheline liquid phase, so that the performance of the support body is affected, and most alkaline substances can be removed by adopting acid washing on the basis. On the other hand, the surface humectant composed of glycerin, tung oil, dihydric alcohol and polyethylene glycol is adopted, and because the water locking property of the fly ash particles is poor, after pug extrusion molding, the initial drying rate is high, the drying stress is high, the green body is easy to deform and crack, the composite humectant can delay the initial surface layer moisture drying rate, and meanwhile, the friction force between the green body and the mat can be reduced, so that shrinkage cracking is prevented. The tung oil and the dihydric alcohol in the composite humectant are used as benign solvents, so that the glycerin can be fully dissolved and dispersed, meanwhile, the lubricating property of the surface of the green body can be improved by the tung oil, the polyethylene glycol provides certain consistence and viscosity for the solution, and the glycerin serving as a main moisturizing component has the function of adsorbing moisture, so that the drying of the green body can be delayed by utilizing the moisture in the air.
As a preferable scheme, the alkaline washing liquid used for alkaline washing comprises 2-4wt% of sodium hydroxide solution or 15-25wt% of sodium carbonate solution, and the solid-liquid ratio of alkaline washing is 1 kg:1.5l-1 kg:3l. The preferable alkali washing liquid in the alkali washing process can effectively destroy silicate glass network, has obvious effect on glass beads, and can solve the influence of the existence of the glass beads in the fly ash on the sintering process.
As a preferable scheme, the pickling solution used for pickling comprises 1-3 wt% of citric acid solution, 3-7 wt% of hydrochloric acid solution, 1-5 wt% of sulfuric acid solution or 0.5-3 wt% of nitric acid solution, and the pickling solid-liquid ratio=1 kg:0.5 l-1 kg:2.5l. The acid liquor is mainly used for removing metals such as iron and calcium or alkaline oxides in the fly ash in the acid washing process, the acid concentration is preferably controlled at a lower level, and part of alkaline substances in the fly ash can be kept as fluxing agent, so that the purpose of reducing sintering temperature is achieved.
As a preferred embodiment, the raw materials include pretreated fly ash, plastic clay, pore-forming agent, low-temperature binder, water, lubricant, water retention agent, water reducing agent and release agent.
As a preferable scheme, the raw materials comprise the following components in parts by mass: 80-95 parts of pretreated fly ash, 6-9 parts of plastic clay, 5-8 parts of pore-forming agent, 2-4 parts of low-temperature binder, 20-28 parts of water, 1-2 parts of lubricant, 2-4 parts of water-retaining agent, 0.5-1 part of water reducer and 0.1-0.3 part of release agent.
As a preferable scheme, in the process of mixing the raw materials, the pretreated fly ash and the plastic clay are mixed firstly, then the water reducer is added for mixing, then the water-retaining agent and the lubricant are added for mixing, then the pore-forming agent and the low-temperature binder are added for mixing, and finally the release agent is added for mixing. The addition sequence of the components in the mixing process can lead organic components such as the water reducer and the like to wrap fly ash particles in advance to form a layer of wettable film, thereby improving the water reducing effect of the water reducer, effectively reducing the water demand of mud materials, slowing down the water loss rate of the green body in the initial drying stage due to the reduction of the water demand, and controlling the generation of drying defects. Further preferred scheme is that the pretreated fly ash and the plastic clay are mixed for 25-35 min, then the water reducer is added for mixing for 3-8 min, the water retention agent and the lubricant are added for mixing for 3-8 min, the pore-forming agent and the low-temperature binder are added for mixing for 3-8 min, and finally the release agent is added for mixing for 5-10 min.
As a preferred embodiment, the plastic clay includes at least one of sozhou soil and granite powder.
As a preferred scheme, the pore-forming agent comprises at least one of corn starch and wood dust.
As a preferred embodiment, the low temperature binder comprises cellulose.
As a preferred embodiment, the lubricant comprises long chain fatty acid methyl esters.
As a preferred embodiment, the water reducing agent comprises lignosulfonate.
As a preferred embodiment, the water-retaining agent includes at least one of polyethylene glycol and water glass.
As a preferred embodiment, the release agent comprises a silicone emulsion.
As a preferable scheme, the surface water-retaining agent consists of glycerin, tung oil, dihydric alcohol and polyethylene glycol according to the mass ratio of 1-2.5:2-4:0.3-0.7:0.5-1. If the proportion of the glycerol relative to the tung oil and the dihydric alcohol is low, the moisturizing effect of the water-retaining agent is poor, if the proportion of the glycerol relative to the tung oil and the dihydric alcohol is too high, a uniform dispersion solution is difficult to form, the moisturizing effect of the glycerol cannot be fully exerted, the glycerol is difficult to fully dissolve and disperse, the moisturizing effect of the glycerol cannot be fully exerted, and the addition amount of the polyethylene glycol can effectively adjust the consistency and viscosity of the surface water-retaining agent to be in a proper range.
As a preferable scheme, the spraying amount of the surface water-retaining agent on the surface of the green body is 5-10 g/0.1m 2 . For example, taking 1000mm x 100mm support body as an example, the weight gain after spraying is 6-8 g.
As a preferable scheme, the conditions of the standing maintenance are as follows: the temperature is 20-25 ℃, the humidity is 25+/-5%rh, and the time is 8-12 h.
As a preferable scheme, the drying adopts microwave drying, the temperature of the microwave drying is 160-180 ℃ and the time is 1-3 h. The microwave drying is carried out under the condition of using the surface water-retaining agent, so that the drying rate can be further controlled, the consistency of the drying rate inside and outside the blank body is ensured, and the generation of cracks is inhibited.
As a preferable scheme, the sintering adopts a buried sintering and low-temperature slow sintering mode; alumina sand and/or zirconia sand are used as buried firing sand, and the low-temperature slow firing process comprises the following steps: the temperature range is 25-180 ℃, the temperature rising rate is 0.5-1.5 ℃/min, the temperature range is 180-550 ℃, the temperature rising rate is 0.2-0.8 ℃/min, the temperature is kept at 550 ℃ for 30-90 min, the temperature range is 550-900 ℃, the temperature rising rate is 3-4 ℃/min, the temperature range is 900-1350 ℃, the temperature rising rate is 3-5 ℃/min, and the temperature is kept at 1350 ℃ for 1.5-2.5 h. By adopting the buried firing process, the blank body can be uniformly heated during firing, the firing performance uniformity of the support body is improved, the uniform discharge of the organic matter combustion gas in the blank body can be controlled, and the firing cracking is reduced. Further preferably, the median diameter of the buried sintered sand is 30 to 45. Mu.m.
The fly ash particles of the invention are ground and sieved by an airflow grinder and an airflow classifier to obtain the particles with the granularity of 9-10.5 mu m.
The preparation process of the fly ash-based support body provided by the invention comprises the following specific steps:
1) Performing alkaline washing and acid washing pretreatment on the fly ash to obtain pretreated fly ash;
2) Firstly adding inorganic raw materials such as pretreated fly ash, plastic clay and the like, mixing for 25-35 min by a counter-current mixer, weighing a water reducer, adding powder, mixing for 3-8 min, weighing a water-retaining agent, adding a lubricant, mixing for 3-8 min, adding organic powder such as a pore-forming agent, a low-temperature binder and the like, mixing for 3-8 min, and finally adding a release agent into the powder, and continuing mixing for 5-10 min to obtain a mixed pug;
3) Aging the mixed pug at 20-25 ℃ for 18-32 h, extruding and molding, firstly performing first pugging under the pressure of 2-3 MPa, then performing second pugging under the condition that the vacuum degree is 0.1 atmosphere, aging for 4-6 h after the second pugging is completed, and starting molding to obtain a green body;
4) After spraying a surface humectant on the surface of the green body, curing for 8-12 hours under the constant temperature and humidity environment with the temperature of 20-25 ℃ and the humidity of 25+/-5%rh, realizing the stability and controllability of the consistency of the drying rate and the internal and external drying rate, reducing the drying cracking phenomenon of the green body, and drying by using microwaves with the temperature of 160-180 ℃ for 1-3 hours; the surface water-retaining agent is formed by mixing glycerol, tung oil, dihydric alcohol and polyethylene glycol according to the ratio of 1-2.5:2-4:0.3-0.7:0.5-1,
5) The dry green body adopts a buried firing and low-temperature slow firing mode, and the low-temperature slow firing process comprises the following steps: the temperature range is 25-180 ℃, the temperature rising rate is 0.5-1.5 ℃/min, the temperature range is 180-550 ℃, the temperature rising rate is 0.2-0.8 ℃/min, the temperature is kept at 550 ℃ for 30-90 min, the temperature range is 550-900 ℃, the temperature rising rate is 3-4 ℃/min, the temperature range is 900-1350 ℃, the temperature rising rate is 3-5 ℃/min, and the temperature is kept at 1350 ℃ for 1.5-2.5 h; realizes the high-temperature controllable elimination of organic matters and prevents the self-ignition of firing.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
according to the preparation method of the fly ash-based ceramic membrane support, provided by the invention, through the alkaline washing and acid washing pretreatment of the fly ash, iron, calcium and other metals or alkaline oxides and carbon particles in the fly ash raw materials can be removed, the surfaces of raw fly ash particles are smooth and compact, the surfaces of the treated fly ash particles become rough, a plurality of grooves and holes are formed, the specific surface area of the particles is increased, the particles are convenient to contact, a sintering phase is easy to form during sintering, the sintering temperature can be reduced, meanwhile, the silicate glass network in the fly ash can be directly damaged, the effect of glass beads is obvious, and the influence of the glass beads on sintering can be effectively avoided.
According to the preparation method of the fly ash-based ceramic membrane support, provided by the invention, through optimizing and adjusting the addition sequence of each component in the mixture, organic components such as the water reducer and the like can wrap fly ash particles in advance to form a layer of wettable film, the water reducing effect of the water reducer is improved, the water demand of pug is effectively reduced, the water loss rate of a blank in the initial drying stage is slowed down due to the reduction of the water demand, and the generation of drying defects can be controlled.
According to the preparation method of the fly ash-based ceramic membrane support, the special surface water-retaining agent is used, so that the solvent volatilization rate can be further controlled in the curing and drying processes, the consistency of the drying rate inside and outside the green body is ensured, and the generation of cracks is inhibited.
The preparation method of the fly ash-based ceramic membrane support body provided by the invention can ensure that the green body is heated uniformly during sintering by using the buried sintering and combining a low-temperature slow sintering process, improves the uniformity of sintering performance of the support body, can control the uniform discharge of organic combustion gas in the green body, and reduces sintering cracking.
The surface of the prepared fly ash-based ceramic membrane support body has no cracking phenomenon, uniform color and luster and no obvious shrinkage deformation, and is a qualified fly ash-based ceramic membrane support body product.
Drawings
FIG. 1 is a slurry of fly ash-based ceramic membrane support prepared in example 1; the mud is moderate in softness and hardness and good in plasticity.
FIG. 2 is a fly ash-based ceramic membrane support body prepared in example 1.
FIG. 3 is a fly ash based ceramic membrane support body prepared in example 1.
Fig. 4 is a graph showing that the fly ash-based ceramic membrane support body prepared in comparative example 1 was subjected to drying to develop a large number of transverse cracks. FIG. 5 is a graph showing the fly ash-based ceramic membrane supports (a: comparative example 2, b: example 2) prepared in example 2 and comparative example 2; cracking occurs in sintering, the color of the support is darker, which means that the organic matter is not well discharged, and the shrinkage of the support becomes larger.
FIG. 6 is a slurry of fly ash-based ceramic membrane support prepared in comparative example 3; the pug is harder, loose and low in viscosity, and is unfavorable for molding.
Detailed Description
The following specific examples are intended to further illustrate the present invention, but not to limit the scope of the claims.
The chemical raw materials used in the following examples are conventional commercial raw materials unless otherwise specified.
Example 1
Step 1: grinding and screening the fly ash particles by an airflow grinder and an airflow classifier to obtain fly ash powder with the particle size of 9.5 mu m; the first alkaline wash is carried out with 3% by weight NaOH solution, powder: liquid = 1:2; the second pickling step was carried out using 1.5% by weight of citric acid, powder: liquid = 1:0.8.
Step 2: weighing 80 parts of 9.5 mu m fly ash according to 10g of each part, mixing 6 parts of Suzhou soil for 25min by using a counter-current mixer; weighing 0.7 part of lignosulfonate, and mixing for 5min; weighing 1 part of FAME fatty acid methyl ester with purity of 99.9%, 3 parts of glycerol, and mixing for 5min; weighing 5.5 parts of corn starch and 2 parts of cellulose, and mixing for 5min; 22 parts of 75 ℃ water and 0.3 part of emulsified silicone oil are weighed, stirred for 25min, and then poured into a mixer for mixing for 7min.
Step 3: after ageing the mixed pug for 24 hours at 25 ℃, carrying out extrusion molding, firstly carrying out first pugging under the pressure of 3MPa, then carrying out second pugging by pumping the vacuum to 0.1 atmosphere, ageing for 5 hours after the second pugging is finished, and starting molding.
Step 4: preparing a surface water-retaining agent according to glycerol, tung oil, dihydric alcohol and polyethylene glycol in a ratio of 1:2:0.3:0.5, and uniformly stirring for use; spraying the formed green body at 24 ℃ under 25%rh in a constant temperature and humidity environment and with a surface water-retaining agent, wherein the spraying amount is 6g/0.1m 2 Curing for 10h, and drying at 170 ℃ in microwave drying for 2h.
Step 5: burying the dried blank with alumina sand with granularity of 30 μm, heating at 25-180 deg.c at 1.2 deg.c/min, heating at 180-550 deg.c at 0.4 deg.c/min, maintaining at 550 deg.c for 60min, heating at 550-900 deg.c at 3 deg.c/min, heating at 900-1350 deg.c at 4 deg.c/min, maintaining at 1350 deg.c for 2 hr, and naturally cooling to obtain the final product.
In the preparation process of the fly ash-based ceramic membrane support body, as shown in fig. 1-3, the pug, the green body and the sintered body are shown in fig. 1-3, and the pug has the characteristics of moderate softness, good plasticity and the like, is beneficial to extrusion molding, and has no cracking phenomenon on the surface of the extruded green body, good uniformity and no cracking phenomenon on the surface of the final sintered support body.
Example 2
Step 1: grinding and screening the fly ash particles by an airflow grinder and an airflow classifier to obtain fly ash powder with the particle size of 9.5 mu m; the first alkaline washing step was carried out using a 16wt% sodium carbonate solution, powder: liquid = 1:3; the second pickling step was carried out using 1.5% by weight of nitric acid, powder: liquid = 1:1.5.
Step 2: weighing 95 parts of 9.5 mu m fly ash according to 10g of each part, mixing 9 parts of Suzhou soil for 25 minutes by using a counter-current mixer; weighing 0.7 part of lignosulfonate, and mixing for 5min; weighing 1 part of FAME fatty acid methyl ester with purity of 99.9%, 4 parts of glycerol, and mixing for 5min; weighing 5.5 parts of corn starch and 2 parts of cellulose, and mixing for 5min; 22 parts of 75 ℃ water and 0.3 part of emulsified silicone oil are weighed, stirred for 25min, and then poured into a mixer for mixing for 7min.
Step 3: after ageing the mixed pug for 30 hours at 25 ℃, carrying out extrusion molding, firstly carrying out first pugging under the extrusion pressure of 3MPa, then carrying out second pugging by pumping the vacuum to 0.1 atmosphere, ageing for 5 hours after the second pugging is finished, and starting molding.
Step 4: preparing a surface water-retaining agent according to glycerol, tung oil, dihydric alcohol and polyethylene glycol in a ratio of 2:3:0.6:0.7; spraying the formed green body at 24 ℃ under 25%rh in a constant temperature and humidity environment and with a surface water-retaining agent, wherein the spraying amount is 6g/0.1m 2 Curing for 10h, and drying at 170 ℃ in microwave drying for 2h.
Step 5: burying the dried blank with alumina sand with granularity of 30 μm, heating at 25-180 deg.c at 1 deg.c/min, heating at 180-550 deg.c at 0.5 deg.c/min, maintaining at 550 deg.c for 60min, heating at 550-900 deg.c at 4 deg.c/min, heating at 900-1350 deg.c at 5 deg.c/min, maintaining at 1350 deg.c for 1.5 hr, and naturally cooling and taking out.
The surface of the fly ash-based ceramic membrane support prepared by the embodiment also has no cracking phenomenon, the size and the color are uniform, the shrinkage deformation phenomenon is avoided, and the fly ash-based ceramic membrane support is a qualified fly ash-based ceramic membrane support product, and the specific view is shown as b in fig. 5.
Comparative example 1
Step 1: grinding and screening the fly ash particles by an airflow grinder and an airflow classifier to obtain fly ash powder with the particle size of 9.5 mu m; the first alkaline wash is carried out with 3% by weight NaOH solution, powder: liquid = 1:2; the second pickling step was carried out using 1.5% by weight of citric acid, powder: liquid = 1:0.8.
Step 2: weighing 80 parts of 9.5 mu m fly ash according to 10g of each part, mixing 6 parts of Suzhou soil for 25min by using a counter-current mixer; weighing 0.7 part of lignosulfonate, and mixing for 5min; weighing 1 part of FAME fatty acid methyl ester with purity of 99.9%, 3 parts of glycerol, and mixing for 5min; weighing 5.5 parts of corn starch and 2 parts of cellulose, and mixing for 5min; 22 parts of 75 ℃ water and 0.3 part of emulsified silicone oil are weighed, stirred for 25min, and then poured into a mixer for mixing for 7min.
Step 3: after ageing the mixed pug for 24 hours at 25 ℃, carrying out extrusion molding, firstly carrying out first pugging under the pressure of 3MPa, then carrying out second pugging by pumping the vacuum to 0.1 atmosphere, ageing for 5 hours after the second pugging is finished, and starting molding.
Step 4: the formed green body is maintained for 10 standing for 2 hours under the constant temperature and humidity environment of 24 ℃ and 25%rh, and then is dried for 2 hours at 170 ℃ in microwave drying.
The comparative example is that the surface water-retaining agent is not sprayed on the surface of the green body of the fly ash-based ceramic membrane support body, a large number of transverse cracks appear after the green body is directly dried, and as shown in fig. 4, the fly ash-based ceramic membrane support body with no surface cracks cannot be obtained by further sintering.
Comparative example 2
Step 1: grinding and screening the fly ash particles by an airflow grinder and an airflow classifier to obtain fly ash powder with the particle size of 9.5 mu m; the first alkaline washing step was carried out using a 16wt% sodium carbonate solution, powder: liquid = 1:3; the second pickling step was carried out using 1.5% nitric acid, powder: liquid = 1:1.5.
Step 2, weighing 95 parts of 9.5 mu m fly ash and 9 parts of Suzhou soil according to 10g of each part, and mixing for 25 minutes by using a counter-current mixer; weighing 0.7 part of lignosulfonate, and mixing for 5min; weighing 1 part of FAME fatty acid methyl ester with purity of 99.9%, 4 parts of glycerol, and mixing for 5min; weighing 5.5 parts of corn starch and 2 parts of cellulose, and mixing for 5min; 22 parts of 75 ℃ water and 0.3 part of emulsified silicone oil are weighed, stirred for 25min, and then poured into a mixer for mixing for 7min.
Step 3: after ageing the mixed pug for 30 hours at 25 ℃, carrying out extrusion molding, firstly carrying out first pugging under the extrusion pressure of 3MPa, then carrying out second pugging by pumping the vacuum to 0.1 atmosphere, ageing for 5 hours after the second pugging is finished, and starting molding.
Step 4: preparing a surface water-retaining agent according to glycerol, tung oil, dihydric alcohol and polyethylene glycol in a ratio of 2:3:0.6:0.7; spraying the formed green body at 24 ℃ under 25%rh in a constant temperature and humidity environment and with a surface water-retaining agent, wherein the spraying amount is 6g/0.1m 2 Curing for 10h, and drying at 170 ℃ in microwave drying for 2h.
Step 5: heating the firing system at 25-550 ℃ at 2.5 ℃/min, heating the firing system at 550-900 ℃ at 5 ℃/min, heating the firing system at 900-1350 ℃ at 5 ℃/min, preserving the temperature for 1.5h, and taking out after natural cooling.
The comparative example does not adopt a burn-in process, and can obviously show that the fly ash-based ceramic membrane support body blank is cracked after sintering, the color of the support body is darker, the organic matter is not discharged well, the shrinkage rate of the support body is increased, and the size is larger than the designed size.
Comparative example 3
Step 1: weighing 95 parts of 9.5 mu m fly ash according to 10g of each part, mixing 9 parts of Suzhou soil for 25 minutes by using a counter-current mixer; weighing 0.7 part of lignosulfonate, and mixing for 5min; weighing 1 part of FAME fatty acid methyl ester with purity of 99.9%, 4 parts of glycerol, and mixing for 5min; weighing 5.5 parts of corn starch and 2 parts of cellulose, and mixing for 5min; 22 parts of 75 ℃ water and 0.3 part of emulsified silicone oil are weighed, stirred for 25min, and then poured into a mixer for mixing for 7min.
Step 2: after ageing the mixed pug for 30 hours at 25 ℃, carrying out extrusion molding, firstly carrying out first pugging under the extrusion pressure of 3MPa, then carrying out second pugging by pumping the vacuum to 0.1 atmosphere, ageing for 5 hours after the second pugging is finished, and starting molding.
Step 3: preparing a surface water-retaining agent according to glycerol, tung oil, dihydric alcohol and polyethylene glycol in a ratio of 2:3:0.6:0.7; and (3) spraying and curing the formed green body for 10 hours at the temperature of 24 ℃ under the constant temperature and humidity environment of 25%rh and the surface water-retaining agent, and then drying for 2 hours at the temperature of 170 ℃ in microwave drying.
Step 4: the dried green body is buried and burned by alumina sand with granularity of 30 mu m, the burning system is heated at 25-180 ℃ at 1 ℃/min, the temperature is heated at 180-550 ℃ at 0.5 ℃, the temperature is kept at 550 ℃ for 60min, the temperature is kept at 550-900 ℃ at 4 ℃/min, the temperature is kept at 900-1350 ℃ at 5 ℃/min, the temperature is kept at 1350 ℃ for 1.5h, and the green body is taken out after natural cooling.
The comparative example mainly comprises that the fly ash is not subjected to washing pretreatment, and the batching modes are different, so that the prepared pug is harder, loose and low in viscosity, and is not beneficial to molding, and the specific pug state is shown in figure 6.
Claims (6)
1. A preparation method of a fly ash-based ceramic membrane support body is characterized by comprising the following steps: the method comprises the following steps:
1) Performing alkaline washing and acid washing treatment on the fly ash to obtain pretreated fly ash; the alkaline washing liquid adopted in the alkaline washing is 2-4wt% of sodium hydroxide solution or 15-25wt% of sodium carbonate solution, and the solid-liquid ratio of the alkaline washing is 1 kg:1.5L-1 kg:3L; the pickling solution adopted in the pickling is 1-3wt% of citric acid solution, 3-7wt% of hydrochloric acid solution, 1-5wt% of sulfuric acid solution or 0.5-3wt% of nitric acid solution, and the pickling solid-liquid ratio=1kg:0.5L-1kg:2.5L;
2) Mixing the raw materials, ageing and extruding to obtain a green body; the raw materials comprise the following components in parts by mass: 80-95 parts of pretreated fly ash, 6-9 parts of plastic clay, 5-8 parts of pore-forming agent, 2-4 parts of low-temperature binder, 20-28 parts of water, 1-2 parts of lubricant, 2-4 parts of water-retaining agent, 0.5-1 part of water reducer and 0.1-0.3 part of release agent;
3) Spraying a surface water-retaining agent on the surface of the green body, standing and curing in a constant temperature and humidity environment, and drying and sintering after curing; the surface water-retaining agent consists of glycerin, tung oil, dihydric alcohol and polyethylene glycol according to the mass ratio of 1-2.5:2-4:0.3-0.7:0.5-1.
2. The method for preparing the fly ash-based ceramic membrane support according to claim 1, wherein the method comprises the following steps: in the mixing process of the raw materials, the pretreated fly ash and the plastic clay are firstly mixed, then the water reducer is added for mixing, then the water-retaining agent and the lubricant are added for mixing, then the pore-forming agent and the low-temperature binder are added for mixing, and finally the release agent is added for mixing.
3. The method for preparing the fly ash-based ceramic membrane support according to claim 2, wherein the method comprises the following steps: the plastic clay comprises at least one of Suzhou soil and granite powder;
the pore-forming agent comprises at least one of corn starch and wood dust;
the low temperature binder comprises cellulose;
the lubricant comprises long chain fatty acid methyl esters;
the water reducer comprises lignosulfonate;
the release agent comprises silicone emulsion.
4. The method for preparing the fly ash-based ceramic membrane support according to claim 1, wherein the method comprises the following steps: the spraying amount of the surface water-retaining agent on the surface of the green body is 5-10 g/0.1m 2 。
5. The method for preparing the fly ash-based ceramic membrane support according to claim 1, wherein the method comprises the following steps: the conditions of standing and curing are as follows: the temperature is 20-25 ℃, and the humidity is 25+/-5%rh; the time is 8-12 h;
the drying adopts microwave drying, the temperature of the microwave drying is 160-180 ℃ and the time is 1-3 h.
6. The method for preparing the fly ash-based ceramic membrane support according to claim 1, wherein the method comprises the following steps: the sintering adopts a buried sintering and low-temperature slow sintering mode; alumina sand and/or zirconia sand are used as buried firing sand, and the low-temperature slow firing process comprises the following steps: the temperature range is 25-180 ℃, the temperature rising rate is 0.5-1.5 ℃/min, the temperature range is 180-550 ℃, the temperature rising rate is 0.2-0.8 ℃/min, the temperature is kept at 550 ℃ for 30-90 min, the temperature range is 550-900 ℃, the temperature rising rate is 3-4 ℃/min, the temperature range is 900-1350 ℃, the temperature rising rate is 3-5 ℃/min, and the temperature is kept at 1350 ℃ for 1.5-2.5 h.
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